Novel organofunctional silicon compounds substituted with halogen and processes for making same

ABSTRACT

Novel organofunctional silicon compounds including silanes of the formula

United States Patent Omietanski 51 Sept. 26, 1972 [54] NOVELORGANOFUNCTIONAL SILICON COMPOUNDS SUBSTITUTED WITH HALOGEN ANDPROCESSES FOR MAKING SAME [72] Inventor: George M. Omletanski, Marietta,

Ohio

[73] Assignee: Union Carbide Corporation [22] Filed: June 11, 1968 [21]Appl. No.: 735,986

[52] US. Cl. ..260/448.2 B, 106/13, 117/126 GQ, 117/126 GS, 127/30,252/49.6, 252/78,

252/351, 252/DIG. l, 260/46.5 E, 260/46.5

G, 260/46.5 Y, 260/209 R, 260/210 R,

E, 260/448.2 N, 260/448.2 R, 260/448.8 R

[51] Int. Cl. ..C07f 7/08, C07f 7/10, C07f 7/18 [58] Field of Search.....260/448.2 B, 448.2, 448.2 N, 260/448.8 R, 398, 408, 46.5 Y, 448.2 E

[56] References Cited UNITED STATES PATENTS 3,132,117 5/1964 Schmidt..260/448.2 X

FOREIGN PATENTS OR APPLICATIONS 713,075 7/1965 Canada ..260/348 PrimaryExaminer-Tobias E. Levow Assistant Examiner-P. F. Shaver Attorney-PaulA. Rose, Aldo John Cozzi, Eugene C. Trautlein, George A. Skoler andReynold J. Finnegan [5 7] ABSTRACT Novel organofunctional siliconcompounds including silanes of the formula and siloxane polymers andcopolymers containing the unit of the formula wherein R, R and R" areorganic groups, Y is divalent oxygen, divalent sulfur, or divalentnitrogen groups, i.e.,

26 Claims, No Drawings 1 2 NOVEL ORGANOFUNCTIONAL SILICON wherein a isan integer of l to 3; b is an integer of l to 6; COMPOUNDS SUBSTITUTEDWITH HALOGEN c is an integer of l to 4; d is an integer of to 3; e is anAND PROCESSES FOR MAKING SAME integer of 1 to 3; f is an integer of 0 to2; R is a radical i free of aliphatic unsaturation having a valence of 1to 6, This invention relates to novel organofunctional sil- 5 saidvalence being equal in the case of said silanes to b icon compoundshaving, bonded to silicon by carbontimes c divided by a and in the caseof said siloxane to-silicon bond, a hydrocarbon group having a halogenpolymers and copolymers to b times e divided by a, R atom and an organicgroup, bonded through oxygen, being selected from the class consistingof hydrogen,

sulfur or nitrogen, attached to adjacent carbon atoms monovalenthydrocarbon groups having one to 18 carof the hydrocarbon group. Theinvention is also b atoms per group, substituted monovalent directed tonovel processes for making such novel comhydrocarbon groups having oneto 18 carbon atoms per pounds. group substituted with substituents fromthe class con- This invention is based on the discovery that orsistingof halogen, alkoxy, cyano, nitro and hydroxy ganofunctional siliconcompounds containing, bonded groups; substituted monovalent hydrocarbongroups to silicon by carbon-to-silicon linkage, at least oneorsubstituted with a substituent having the formula ganofunctional groupcontaining an organic group, R O(C,,H ,,O) wherein R is a monovalentbonded through oxygen, sulfur or nitrogen, and a hydrocarbon grouphaving one to 18 carbon atoms, n is halogen atom which are attached tovicinal carbon an integer of 2 to 4, andx is an integer of l to 100, andatoms of a hydrocarbon group bonded to silicon can be having one to 18carbon atoms per group in addition to made by reacting an olefinicallyunsaturated silicon 20 those in said substituent; acyl groups having oneto 18 compound, a protolytic or active hydrogen atom concarbon atoms pergroup; substituted acyl groups subtaining compound and a positivehalogen compound as stituted with a substituent from the classconsisting of shown by the equations: hydroxy, alkoxy groups having oneto 18 carbon atoms per alkoxy group, and R O(C,,H ,,O) groups and amymbRo s l/ R R/) s RIl HZ having one to 18 carbon atoms per group inaddition to 3 those of said substituent; divalent hydrocarbon groupshaving two to 18 carbon atoms; divalent groups of the l!) formula{- Cl-l O),,C,,H divalent groups of the forwherein R is a divalenthydrocarbon group having two to 18 carbon atoms per group; divalentgroups of the formula wherein R( Yl-l),, and R(YH) are protolyticcompounds, R SiR and R,Si(R"),O are the olefinically unsaturated silaneand siloxane, respectively, and X Z- is the positive halogen compoundwherein X is halogen of an atomic weight of at least 19, Z is thenegative part of the positive halogen compound and 40 0 i) HZ is itshydrogenated form by-produced in the reactron.

More specifically, the following equations illustrate the reaction oftrifluoroethanol, t-butyl hypochlorite and, respectively,vinyltrimethylsilane and 3-vinylhepwherein R is a divalent hydrocarbongroup having two to 18 carbon atoms per group; divalent groups of theformula tamethylsiloxane: L 0 R C R4C Ln (i) y u (3) 0 x 0 c F3CH2OHcmzc s divalent groups of the formula imr-rmoooi 50 -R0 OR4COR50 CR4C;CF3CH2OCH2CIIC1S1ME3 (CH3)3COH g trivalent hydrocarbon groups having 3to 18 carbon C FCHEOH CHFCHsiMMOSiMem atoms per group; trivalent groupsof the formula (CHa)aCOCl Hic(0o,.Hz., OF CHzOCHgCHClSiMe(OSiMes)z(CHmOOH H2C(OC Hz /X The novel organofunctional silicon compoundsinclude silanes of the formula: X trivalent groups of the formula "d],Ru L and siloxane polymers and copolymers containing the J unit of theformula:

(I!) R RH 5 wherein R is a trivalent hydrocarbon group having three to18 carbon atoms per group; tetravalent 1 hydrocarbon groups having threeto 18 carbon atoms b per group; tetravalent groups of the formulapentavalent hydrocarbon groups having four to 18 carhexavalenthydrocarbon groups having four to 18 carbon atoms per group andhexavalent groups of the formula l on 0 cum) Y is a divalent elementselected from the group consistin g of O-,

and S- wherein R' is selected from the group consisting of hydrogen andmonovalent hydrocarbon having one to 18 carbon atoms; R is a divalenthalogensubstituted hydrocarbon group having two to 18 carbon atomsselected from the class consisting of alkylene, cycloalkylene andalkylenearylene groups, wherein said halogen substituent and saiddivalent element are bonded to adjacent non-aromatic carbon atoms; R" isa monovalent organic group bonded to silicon and is selected from theclass consisting of hydrocarbon groups, alkoxy groups, aryloxy groups,substituted hydrocarbon groups substituted with a substituent from theclass consisting of halogen, alkoxy, acyl, acyloxy, cyano, nitro andhydroxy substituents, all of said groups having a total of one to 18carbon atoms per group; R (C,,H ,,O) C,,H groups wherein R, n and x areas defined above and substituted hydrocarbon groups substitutedhydrocarbon groups substituted with a R O(C,,H ,,O), substituent andhaving one to l 8 carbon atoms in addition to the carbon atoms in saidsubstituent.

The novel siloxanes containing siloxy units of formula (B) can alsocontain siloxy units of the formula:

wherein R is as defined above and g is an integer of 0 to 3. Typical ofthe units represented by formula (C) are the SiO:, monomethylsiloxy,dimethylsiloxy, trimethylsiloxy, monophenylsiloxy, methyl[butoxypoly(oxyethyleneoxypropylene )propyl jsiloxy, diphenylsiloxy,triphenylsiloxy, methyl(methoxypolyoxyethylenepropyl)siloxy,beta-phenylethylsiloxy, methyl( hydrogen )-siloxy andmethyl(ethyl)siloxy units. The novel siloxanes can contain 1 to 100 molpercent, preferably 10 to 60 mol percent, of units of formula (B) and 0to 99 mol percent, preferably 40 to 90 mol percent, of units of formula(C).

Typical R groups shown in formulas (A), (B) and (C) are alkyl orcycloaliphatic groups, such as, methyl, ethyl, propyl, cyclopentyl,butyl, amyl, octyl, cyclohex- 0 yl, isopropyl, tert-butyl, octadecyl,isooctyl and the like, aryl groups, such as, phenyl, biphenyl, naphthyland the like, aralkyl groups, such as, benzyl, beta-phenylethyl,beta-phenylpropyl, substituted aryl groups, e.g., halogen-substituted,alkoxy-substituted and aryloxy-substituted aryl groups, such as,chlorophenyl,

trifluoromethylphenyl, phenoxyphenyl, chloronaphthyl, anisyl and thelike, substituted aralkyl groups, e.g., halogen-substituted,alkoxy-substituted and aryloxy-substituted aralkyl groups, such as,chlorobenzyl, beta-anisylethyl, beta-phenoxynaphthylpropyl and the like,substituted alkyl groups, e.g., halogen-substituted, alkoxy-substituted,cyano-substituted and aryloxy-substituted alkyl groups, such as,gamma-chloropropyl, 3,3,3-trifluoropropyl, betacyanoethyl,gamma-methoxypropyl, and alkyl groups substituted with other functionalgroups which do not contain an active hydrogen, olefinic hydrocarbongroups, e.g., alkenyl and cycloalkenyl groups, such as,

vinyl, allyl, 2-butenyl, cyclohexenyl, and the like.

The siloxane polymers containing siloxy units of the formula (B) with orwithout units of formula (C) can also contain silcarbane groups such asE Si(CH ),,Si E and E SiC l-l Si E groups, wherein at least one of thesilicon bonds of said silcarbane groups is connected through Si-OSilinkage to a siloxy groups of formula (B) or (C), if present in thepolymer, and the remaining silicon bonds of the silcarbane group arebonded in the same way or to an R" group.

0 When there are two or more R groups in the molecu e of the novelcompounds of this invention, such R groups may be the same or differentin the same molecule. When there are two or more YR' groups in the samemolecule, they also may be the same or different and when there are twoor more R" groups in the same molecule, they too can be the same ordifferent. When there are two or more siloxy units of formula (B) in thesame molecule, such units can be the same or different throughout thesame molecule.

Likewise, when there are two or more siloxy units of formula (C), suchunits can be the same or different in the same molecule.

According to our studies the reactions depicted in equations l) and (2)are general and are applicable to 5 all organosilicon compounds havingolefinic unsaturation. Typical olefinically unsaturated silanes arerepresented by the formula: 0 R SiR" and typical siloxanes arerepresented by the formula:

E )l (4 e fl 2) with or without units of formula (C) wherein R", c, d, e

and f are as defined above and R is an olefinically unsaturated organicgroup bonded to silicon by silicon-tocarbon bond, such as, alkenyl,e.g., vinyl, allyl, oleyl and the like, cycloalkenyl, e.g.,cyclopentenyl,

Protolytic compounds, R YH and R YH useful in this invention includehydroxy compounds, such as, water, alcohols, polyols, phenols,carboxylic acids, polycarboxylic acids, and the like.

The alcohols and phenols may be monomeric or polymeric and may berepresented by ROI-I where R is as defined above including alkanols,e.g., methyl, ethyl, i-propyl, t-butyl, cyclohexyl, octadecyl alcoholsand the like; substituted alkanols, substituted with halogen, alkoxy,cyano, nitro, hydroxy, or R O(C,,H ,,O), groups wherein R n and x are asdefined above, e.g., 2,2,2-trifluoroethyl, l H, l H-perfluorooctyl, 2-cyanoethyl, 2-cyano-2-propyl, l,l,l-tribromo-2- methyl-Z-propyl,2-(2-methoxyethoxy)ethyl alcohols and the like; aryl and substitutedaryl hydroxy compounds, e.g., phenol, toluol, p-chlorophenol, 2,4,6-tribromophenol, m-nitrophenol, and the like; aralkanols, e.g., benzylalcohol, cinnamyl alcohol, benzhydrol, triphenylcarbinol and the like.It is preferred that the protolytic compound be free of alkenyl oralkynyl groups.

Polyols include di-, tri, or higher hydroxy organic compounds and can bemonomeric or polymeric, e.g., l ,Z-ethanediol, l,2-propanediol;glycerol, pentaerythritol, sorbitol, sucrose, glucose, pinacol,1,2,4-butanetriol, 1,2,6-hexanetriol, 1,10- decanetriol, polyoxyalkyleneglycols l-IO(C,,H ,,O) C H OH, e.g., HO(C H O) H, sorbitol startedpolyalkylene-oxide adducts, e.g.,

wherein n is 2 or 3 or 4 and x is l to 100, e.g., l, 5, l0, l2 and 18;glycerol started polyalkylene-oxide adducts, e.g.,

l,4-butanediol,

wherein n and x are as described above; pentaerythritol startedpolyalkylene-oxide adducts, such as,

wherein n and x are as defined above; glucose or sorbose startedpolyalkylene-oxide adducts, such as,

wherein n and a; are as defined above; glycol terminated polyesters,such as HOR O ORACOR [II I O wherein R, R and x are as defined above,e.g.,

e.g., the alkanoic acids including acetic acid, octadecanoic acid,formic acid and the like; the substituted alkanoic acids substitutedwith hydroxy, alkoxy, aryl or R O(C,,H ,,O) groups wherein R, n and xare as defined above including methoxyacetic acid, benzoic acid, HOCH COH, trifluoroacetic acid, glutamic acid, gluconic acid, pyruvic acid,salicylic acid, ascorbic acid, HOC H CO H, lactic acid, thioglycolicacid, cyanoacetic acid, phenylacetic acid, chloropropionic acid,bromoacetic acid, and the like. The polycarboxylic acid include HOOCRCOOH wherein R is as defined above, such as, oxalic acid, adipic acid,tartaric acid, malonic acid, succinic acid, phthalic acid, malic acid,tetrahydrophthalic acid, ortho-phenyleneacetic beta-propionic acid,phenylenediacetic acid, hydrocinammic acid, epsilon-phenyl-n-caproicacid, and R (COOH) wherein R is as defined above, such as,carboxysuccinic acid, trimellitic acid, citric acid, trimesic acid,diphenic acid and the like; acid terminated polyesters such as whereinR, R and x are as defined above, e.g.,

ethylene glycol-terephthalate polyesters made from equimolar or greateramounts of dicarboxylic acid and the like.

Protolytic compounds R(YH),,,,,,, and R(Yl-l),, also include amines andmercaptans. The amines have the formula wherein R and R are as definedabove and include methylamine, ethylene diamine, diethylenetriamine,pentaethylenehexamine, aniline, hexamethylenediamine, ethanolamine,diethanolamine, laurylamine, di-n-propylamine, diphenylamine,piperidine, morpholine, diethylamine and the like. The mercaptans havethe formula R(SH)1 wherein R is defined above and includes methanethiol, dodecane thiol, octadecane thiol, orthomercaptobenzoic acid,phenylmercaptan, alpha-toluenethiol, thioacetic acid, thiobenzoic acidand the like.

Positive halogen compounds, X Z, are defined as materials in which thehalogen is the positive end of a dipole in a molecule in which theremainder of the molecule is a nucleophile. (E. S. Gould, Mechanism andStructure in Organic Chemistry, Holt, Rinehart and Winston, 1959, NewYork.) They are considered to be nucleophilic carriers of halogen, i.e.,positive halogen carriers. Examples include: alkyl hypohalites, e.g.,t-butyl hypochlorite, trifluoromethyl hypofluorite, and the like; acylhypohalites, e.g., acetyl hypobromite; N-haloamines, e.g., N,Ndichloro-t-butylarnine; N- haloamides, e.g.,N,N-dibromobenzenesulfonamide, N,N-dichlorobenzenesulfonamide,N-bromo-acetamide, N-chloroacetamide; N-haloimides, e.g., N-chlorophthalimide, N-chlorosuccinimide, N-bromosuccinimide, 1,3-dichloro- ,S-dimethylhydantoin,lbromo-s-triazine-2,4,6(3H,5H)-trione(bromoisocyanuric acid);l-haloalkynes, e.g., l-bromohex-lyne;a-halocarbonyl compounds, e.g.,2,2- dibromomalonic ester, 3,3-dichloropentane-2,4-dione,

halonitromethanes, e. g. chlorotrinitromethane, dibromodinitromethane;halocyanomethanes, e.g., bromotricyanomethane; halomethane, e.g.,

bromotrifluoromethane; haloacylmethanes; activated haloaromaticcompounds, e.g., 2,4,6- trinitrochlorobenzene; nitryl halides, sulfenylhalides, e.g., trichloromethanesulfenylchloride. The molecular halogensand interhalogen compounds excluding molecular fluorine are also usefulas sources of positive halogen: C1 Br ClBr, BrI as well as the inorganichypohalites, e.g., NaOBr, Ca(OCl) LiOCl. Any of the above compounds canbe used herein.

Other suitable positive halogen compounds are oxyalkylene hypohalites,which are represented by the formula: RO(C,,H ,,O COX wherein R is X orR as defined above, X is a halogen having an atomic weight ofat least19, n has a value offrom 2 to 4 andx has a value of from 1 to about 100,preferably n is 2 or 3. Copolymers where n is a mixture of ethylene andpropylene units are also suitable.

The process of this invention requires one equivalent of positivehalogen from the positive halogen compound per mol of olefinic groupconnected to silicon for complete reaction of the olefinic unsaturationof the silicon compound. The positive halogen compound and siliconcompound can be brought together in any ratio depending on the effectdesired or product sought. A 1:1 ratio is preferred as an excess ofpositive halogen compound may lead to undesirable side reactions, e. g.,excess halogenation of product, especially in the presence of hydroxyliccompounds that are not too difficult to halogenate, such as ethanol. Adeficiency of positive halogen leads to incomplete reactions.

With added protolytic materials, the positive halogen compound promotesthe addition of the protolytic material with little if any production ofproduct which normally would be formed from the positive halogencompound and silicon compound. The silicon compound, the protolyticmaterial and positive halogen compound may be brought together in anyratio whatsoever, the chosen ratio depending on the effect desired orproduct sought. The preferred ratio of positive halogen compound toolefinically unsaturated silicon compound is 1:1 with an excess ofprotolytic compound. With an excess of either the protolytic material orthe silicon compound, the positive halogen compound preferably should beequimolar with the limiting reagent.

The ratio of added protolytic material to positive halogen compound andolefinically unsaturated silicon compound is important. The rate ofreaction, yield and purity of adduct are increased with larger excessesof protolytic material. Examples 1 and 4 illustrate that at a 6:121ratio, reaction time was 30 minutes and yield of adduct was 75 percent;Whereas at 1:1:1 ratio, reaction time was two months and yield ofadducts was 53 percent. These effects are also illustrated in Examples15, 16 and 17.

Catalysts are not required but may be used, if desired, to improvereaction times and yields. Addition of protolytic compounds havingacidic hydroxylic groups, e.g., 2,2,2-trifluoroethanol, acetic acid,phenol, etc., are catalyzed by basic materials, e.g., potassiumtbutoxide, potassium silanolate, tetramethyl ammonium silanolate,pyridine, bis-triphenylphosphine platinum (II) chloride,triphenylphosphine and pyridine-N oxide. Examples 1 and 2 illustrate thereduction in time of reaction from 4 days to 30 minutes by the use ofcatalysts. Many other basic materials and possibly other classes ofcompounds would also be effective.

Reactions of essentially neutral protolytic materials, e.g., methanol,ethanol, 2-propanol and 2-methoxyethanol were catalyzed by cupricacetate and benzene-sulfonic acid. For 2-methoxyethanol, cobalticacetate was found to be a catalyst.

Solvents are not required but may be used if desired, especially formaking reactants compatible and for moderating those reactions whichproceed rapidly and exothermically. Any organic solvent that does notcontain active hydrogen atoms may be used. Such solvents include thealiphatic and aromatic hydrocarbons, ketones, esters, nitriles and nitrocompounds. The preferred solvents are the hydrocarbons, e.g., n-hexane,benzene, toluene; chlorinated hydrocarbons, e.g., dichloromethane,carbon tetrachloride, esters, e.g., ethyl acetate and nitrobenzene.

Any sequence of mixing may be used for the reactants. Since positivehalogen compounds readily chlorinate many organic materials, thepreferred order of addition is to introduce the positive halogencompound to a mixture of the olefinically unsaturated silicon compoundand the protolytic material. It may also be desired to control the rateand temperature of reaction by the rate of addition of the positivehalogen compounds.

The process of this invention may be carried out over a wide range ofconditions. It may be accomplished at temperatures from l00 to 200C, theonly limit being the decomposition temperature of the reactants,especially the positive halogen compound. Pressures above, below or atatmospheric pressures may be used. The preferred reaction conditions areat atmospheric pressure and from 70 to 100C. During the reaction, it ispreferred that light be excluded.

Reaction time varies from a few minutes to a few days depending uponboth the positive halogen compounds, and the protolytic material used,the catalyst and also temperature. When the positive halogen compound isemployed in a 1:1 molar ratio of positive halogen to olefmicallyunsaturated group, the reaction can be followed by measuring thepresence or absence of positive halogen.

The process of this invention is superior to heretofore known methods ofpreparing organofunctional silicones in that there results (1) improvedyields, (2) shorter reaction times, (3) greater versatility and (4) lowreaction temperatures. The present invention provides advantageousprocedures for preparing a wide range of organofunctional materials. Forexample, the present invention permits the preparation of resinous orrubbery materials at ambient temperatures, thus providing novel coating,potting and molding compositions.

The novel monomeric and polymeric compounds produced by the process ofthe present invention are useful as intermediates in the production oforganofunctional silicon compounds and other organic derivativesthereof. The liquid monomers of this invention can be used as sizes forfibrous materials, e.g., for glass fibers and organic textiles to impartwater repellency and lubricity thereto, and as intermediates for theproduction of siloxane polymers and copolymers. The novel siloxanepolymers and copolymers produced as oils are useful themselves aslubricants. Those polymers and copolymers produced as resins are usefulas coatings to prevent corrosion, encapsulating materials for electroniccomponents and the like. Those siloxanes produced as gums are useful inthe production of silicone elastomers in the conventional manner forthose applications in which the well known silicone elastomers areemployed. The novel siloxane polymers and copolymers can be employed asmodifying ingredients for known silicone lubricating oils and to modifysilicone elastomers. The siloxane polymers and copolymers can also beproduced as semi-solids useful in themselves as adhesives and asgrease-modifiers.

The novel siloxane polymers and copolymers made from silicon compoundshaving three or more olefinic groups to the molecule and/or protolyticcompounds having three or more active hydrogen atoms to the molecule arecross-linked in nature and set to solid materials useful as protectivecoatings. Also, the solid polymers and copolymers of this invention canbe used as grease thickeners and as additives or modifying ingredientsfor the known thermosetting polysiloxanes.

Products with very low surface tensions were prepared in the Examplesand are useful as surfactants, defoamers, etc. Silicone-alcohols, whichalso are useful as surfactants, are prepared by the method illustratedin Example 12. A persistent flame retardant additive for silicone rubberwas prepared in Example 14.

The halo group in the products of this invention are useful innucleophile displacement reactions, e.g., in the preparation of ethersby reaction with sodium alkoxides.

In addition, the process of this invention provides an improved methodfor bringing about ambient temperature polymerization and curing oforganosiloxane materials both with and without filler. As shown inExample 20, ethylene glycol and t-butyl hypochlorite cause curing of avinylmethyl-dimethylsiloxane fluid in 1 day. Thus, room temperaturevulcanization systems,

which do not require atmospheric moisture and which have reasonable pourand cure times can be prepared.

Other uses for the process and products of this invention includecoating of fillers, preparation of silicone alkyd resins, sizing ofpaper, treatment of cotton fabric to impart water repellency, and thelike. The fluid products are useful as hydraulic fluids, coolants andlubricants. The solid products are useful, in pulverized condition, asfiller materials in molding compositions, paints, potting compositionsand the like.

The following Examples are presented. In these Examples boiling points,b.p., are in C. measured at the reduced pressure indicated in mm of Hg,MR is molar refraction, using sodium light, R is specific refractionwhich is molar refraction divided by molecular weight (MR /MW), V.P.C.means vapor phase chromatography, the ratios in parentheses in thetitles are the molar ratios of the protolytic material to thealkenylsiloxane to the positive halogen compound, n,, is index ofrefraction using sodium light at 25C., d, is specific gravity measuredat 25C. referred to water at 4C., Ac means the acetyl group, CH C(O), Memeans the methyl group, Et means the ethyl group, t-

Bu means the tertiary butyl group, and 2-Pr means the 2-propyl group.Parts and percentages are by weight.

EXAMPLE 1 Addition of Trifluoroethanol to 3- Vinylheptamethyltrisiloxanewith t-Butyl Hypochlorite (6: 1:1 in Presence of Catalyst In a 500 ml.flask fitted with a sealed stirrer, an addition funnel and an adapterwith thermocouple well and condenser were placed 3-vinylheptamethyltrisiloxane (24.8 grams, 0.1 mol),2,2,2-trifluoroethanol (60.0 g., 0.6 mol) and t-butyl hypochlorite(10.85 g., 0.1 mol) in 120 ml. of anhydrous benzene. The contents of theflask were protected from light by a covering of aluminum foil. Also,the temperature of the contents was continuously recorded. Addition oftwo drops of potassium silanolate (containing 2.9 percent K) caused anexothermic reaction with a 30C. rise in temperature within four minutes.No t-butyl hypochlorite was detected thirty minutes after the additionof catalyst, using starch-iodide test paper. The material was distilledto give 28.8 grams mol-% yield) of 3-[2- (2,2,2-trifluoroethoxyl-chloroethyl ]heptamethyltrisiloxane, b.p. 46/O.l mm., n 1.3973, df1.404, surface tension 20.1 dynes/cm. (Purity by vapor phasechromatography percent.)

Analysis: Calculated for CF CH OCH CHCl- SiMe(OSiMe C, 34.5 percent; H,6.8 percent; Si, 22.0 percent; C], 9.3 percent; F, 14.9 percent; R

0.2309. Found: C, 34.0 percent; H, 6.9 percent; Si, 21.4 percent; CI,9.8 percent; F, 14.6 percent; R

0.2316. Both infrared and nuclear magnetic resonance spectra confirmedthe assigned structure.

EXAMPLE 2 Addition of Trifluoroethanol to 3- Vinylheptamethyltrisiloxanewith t-Butyl Hypochlorite (6:1 :1 Without Catalyst t-Butyl hypochlorite(21.7 grams, 0.2 mol) was added to a solution of3-vinylheptamethyltrisiloxane (49.6 g., 0.2 mol) and2,2,2-trifluoroethanol (120 g., 1.2 mol) in 100 m1. of benzene. Anexothermic reaction resulted (18 temperature rise). After standing 4days, no positive halogen was detected. The material was distilled toyield 54.9 grams (72 mol-% yield) of 3- [2-( 2,2,2-trifluoroethoxy)- l-chloroethyl ]heptamethyltrisiloxane, b.p. 4245/0.1 mm.; n 1.3993(purity by V.P.C. 84 percent).

EXAMPLE 3 Addition of Trifluoroethanol to 3- Vinylheptamethyltrisiloxanewith t-Butyl Hypochlorite (3: 1 :1 in Presence of Catalyst Addition of adrop of potassium silanolate (2.9 percent K) to a solution of 24.8 grams(0.1 mol) of 3-vinylheptamethyltrisiloxane, 15.0 g. (0.15 mol) of 2,2,2-trifluoroethanol and 0.85 g. (0.1 mol) of t-butyl hypochlorite in 110ml. of benzene resulted in an exothermic reaction (9C. rise). After 2hours, the mixture had returned to room temperature but still containedt-butyl hypochlorite, an additional 15 g. (0.15 mol) of trifluoroethanolwas added and an exothermic reaction commenced (6C. rise intemperature). No positive halogen was detected after standing overnight.

After distillation, 3-[2-(2,2,2-trifluoroethoxy)-1-chloroethyllheptamethyltrisiloxane was isolated: 30.5 grams (80 mol-%yield), b.p. 46/0.l mm., n 1.3970 (purity by V.P.C. 86 percent) EXAMPLE4 Addition of Trifluoroethanol to 3- Vinylheptamethyltrisiloxane witht-Butyl Hypochlorite 1: 1:1 in Presence of Catalyst To a mixture of 24.8grams (0.1 mol) of 3-vinylheptamethyltrisiloxane, 10.0 g. (0.1 mol) of2,2,2- trifluoroethanol and 10.85 g. (0.1 mol) of t-butyl hypochloritein 125 ml. of benzene were added two drops of potassium silanolate 2.9percent K). An exothermic reaction resulted (4C. rise). After 1 month,the mixture still contained positive halogen but was free of positivehalogen after an additional six weeks. Distillation gave 20.2 g. (53mol-% yield) of 3-[2- (2,2,2-trifluoroethoxy)- l-chloroethyl]heptamethyltrisiloxane, b.p. 4648/0. 15 mm., n 1.3979(purity by V.P.C. 72 percent).

EXAMPLE 5 Addition of Trifluoroethanol to Vinyltrimethylsilane witht-Butyl Hypochlorite (6: 1: l

To a mixture of 20.04 g. (0.2 mol) of Vinyltrimethylsilane and 120 g.1.2 mol) of 2,2,2-trifluoroethanol in ml. of benzene were added dropwise21.7 g. (0.2 mol) of t-butyl hypochlorite over a 1 hour period. Theexothermic reaction was maintained at 50C. by the rate of addition. Not-butyl hypochlorite was detected within an additional hour. Afterdistillation, 22.4 g. (47 mol-% yield) of 2-(2,2,2-trifluoroethoxy)- 1-chloroethyltrimethylsilane, b.p. 65/ 15 mm., n 1.4083, d 1.1094, wereisolated. (Purity by V.P.C. 94 percent.) Analysis: Calculated for CF CHOCH CHClSiMe C, 35.8 percent; H, 6.0 percent; Si, 11.9 percent; Cl, 15.1percent; F, 24.3 percent; R 0.2175. Found: C, 35.5 percent; H, 6.3percent; Si, 10.8 percent; Cl, 18.6 percent; F, 18.3 percent; R 0.2225.Nuclear magnetic resonance and infrared spectra confirmed the assignedstructure.

EXAMPLE 6 Addition of Trifluoroethanol to 3-( 3-Cyclohexenyl)heptamethyltrisiloxane with t-Butyl Hypochlorite (6:1: 1

t-Butyl hypochlorite (10.85 g., 0.1 mol) was added dropwise over a halfhour period to a solution of 3-(3- cyclohexenyl)heptamethyltrisiloxane(30.25 g., 0.1 mol) and 2,2,2-trifiuoroethanol (60.0 g., 0.6 mol) in 75ml. of benzene. An exothermic reaction resulted (30C. rise) and nopositive halogen was detected after 2 hours. A small amount ofisobutylene was detected in the gas over the reaction. The productsolution was distilled to yield 23.0 g. (53 mol-% yield) of 3-[(2,2,2-trifluoroethoxy-)chlorocyclohexyl]heptamethyltrisiloxane, b.p., 86/0. 15mm., n 1.4092, d 1.0385 (purity by V.P.C. 75 percent). Analysis: Calculated for CF CH OC ClI-l Si(OSiMe C, 41.2 percent; H, 7.4 percent; Si,19.3 percent; Cl, 8.1 percent; F, 13.0 percent; R 0.2398. Found: C, 39.9percent; H, 7.3 percent; Si, 18.4 percent; Cl, 7.7 percent; F, 12.0percent; R 0.2382. Infrared spectrum confirmed the assigned structure.

EXAMPLE 7 Addition of Trifluoroethanol to Vinylmethylcyclosiloxanes witht-Butyl Hypochlorite (6: 1: 1) in Presence of Catalyst To a solution of43 g. (0.5 mol) of Vinylmethylcyclosiloxanes (mostly trimers andtetramers) and 300 g. (3.0 mol) of 2,2,2-trifluoroethanol in 300 g. oftoluene were added 54.3 g. (0.5 mol) of t-butyl hypochlorite.Benzene-sulfonic acid (0.5 g.) was added as catalyst. An exothermicreaction occurred and the temperature rose 15C. After standingovernight, the mixture was distilled to give two fractions of 2-(2,2,2-trifluoroethoxy)- 1 -chloroethylmethylcyclosiloxanes (mostly trimers andtetramers);

1. 18.3 g., b.p. 137190/0.10.7 mm., n 1.4118, d 1.3662; and

2. 38.8 g., b.p. l90205/0.70.5 mm., n 1.4173, d 1.3860. Overall yieldwas 52 mol-%. Analysis: Calculated for CF CH OCH CHClSiMeO: C, 27.2percent; H, 3.7 percent; Si, 12.7 percent; F, 25.8 percent; Cl, 16.1percent; R 0.1793. Found: C, 28.5 percent, 27.7 percent; H, 4.1 percent,3.8 percent; Si, 17 per- 2. The infrared spectra confirmed the assignedstructure.

EXAMPLE 8 Addition of 1H, lH-Perfluorooctanol to 3-Vinylheptamethyltrisiloxane with t-Butyl Hypochlorite (2: l 1) inPresence of Catalyst t-Butyl hypochlorite (4.07 g., 0.0375 mol) wasadded to a mixture (two phases) of 1H, lH-perfluorooctanol (30.0 g.,0.075 mol) and 3-vinylheptarnethyltrisiloxane (9.30 g., 0.0375 mol) inml. of benzene. A few crystals of potassium t-butoxide catalyst had beenadded prior to hypochlorite addition. The reaction was exothermic andafter standing 1 day no positive halogen was detected. The material wasconcentrated and distilled to give 20.4 g. (80 mol-% yield) of 3-[2- 1H, lH-perfluorooctyloxy)- 1 -chloroethyl]heptamethyltrisiloxane, b.p.88/0.1 mm., m, 1.3651 di 1.3001, surface tension, 18.9 dynes/cm. Purityby V.P.C. 80 percent. Analysis: Calculated for C1F 5CH OCHCHC1SiMe(OSiMe3)2 C, 35.2 percent; H, 3.8 percent; Si, 12.3 percent; Cl,5.2 percent; F, 41.7 percent; R, 0.1720. Found: C, 29.8 percent; H, 4.0percent; Si, 11.9 percent; Cl, 5.1 percent; F, 40. 1 percent; R D, 0.1719. Infrared spectrum confirmed the a e Struc ure.

EXAMPLE 9 Addition of Ethanol to Vinylmethyldiethoxy silane with t-ButylHypochlorite (6:1: 1 in Presence of Catalyst t-Butyl hypochlorite (54.0g., 0.5 mol) was added dropwise to a solution ofvinylmethyl'diethoxysilane (80 g., 0.5 mol) in ethanol (132 g., 3.0mols). The reaction 40 was catalyzed by 0.5 g. of benzene-sulfonic acid.An exothermic reaction resulted and was controlled (3055 C.) by rate ofaddition. The reaction was allowed to proceed for 2 hours. Distillationgave 32 g. (27 mol-% yield) of2-ethoxy-1-chloroethylmethyldiethoxysilane, b.p. 97-100/9 mm., n 1.4279,df, 1.020 g/ml: Analysis: Calculated for EtOCl-l CHClSiMe(OEt) C, 44.9percent; H, 8.8 percent; Si, 11.6 percent; Cl, 14.7 percent; R,,,0.2557. Found: C, 43.1 percent; H, 8.5 percent; Si, 11.8 percent; CI,14.7 percent; R 0.2522. Infrared spectrum was in accord with theassigned structure.

EXAMPLE l0 5 Addition of Ethanol to 3-Vinylheptamethyltrisiloxane witht-Butyl Hypochlorite (6: 1 :1 in Presence of Catalyst was-distilled i0give 20.4 g. 62 mol-% yield) of 3 2-ethoxy-l-chloroethyl)heptamethyltrisiloxane, b.p. 48-50/0.1 mm, n1.4185, d 0.9572, purity by V.P.C. 69 percent. Analysis: Calculated forCH,CH,OCH,CHClSiMe (OSiMe,) C, 40.2 percent; H, 8.9 percent; Si, 25.6percent; Cl, 10.8 percent; R,,, "0.2678. Found: C, 38.0 percent; H, 8.4percent; Si, 24.6 percent; C1, 13.1 percent; R,,, 0.2635. The infraredspectrum confirmed the assigned structure.

EXAMPLE 11 Addition of Ethanol to Vinyltn'ethoxysilane with N-Bromosuccinimide 1.1:1:l) Without Catalyst To a mixture of 93.5 g. (0.49mol) of vinyltriethoxysilane and 25.3 g. (0.55 mol) of absolute ethanolwere added 89 g. (0.5 mol) of N-bromosuccinimide with 200 EXAMPLE 12Addition of Ethylene Glycol to vinyltrimethylsilane with t-ButylHypochlorite (3: 1 1) in Presence of Catalyst t-Butyl hypochlorite (21.7g., 0.2 mol) was added to a mixture of vinyltrimethylsilane (20.0 g.,0.2 mol) and 1,2-ethanediol (36.0 g., 0.6 mol) in 50 ml. of an hydrousacetone which contained a few crystals of copper (H) acetate (two phasemixture). After a 5 minute induction period, an exothermic reactionoccurred which was controlled by the rate of addition and externalcooling (maximum temperature 50C.). No positive halogen was detectedafter twenty hours but the mixture was acidic. Anhydrous pyridine (2.0g.) was added and the resulting precipitate removed by filtration.Distillation gave 29.2 g. of2-(2-hydroxyethoxy)-l-chloroethyltrimethylsilane, b.p. 48/0.25 mm., n1.4408, d 1.0942. Found R 0.2412, Calculated R 0.2457. Analysis by gaschromatography showed the product to be a mixture. The two principalcomponents were separated by V.P.C. and infrared scans of the purecomponents were recorded. One of the materials was 2-( 2-hydroxyethoxy l-chloroethyltrimethylsilane and the other was 1,2-ethanediol.

EXAMPLE 13 Addition of Acetic Acid to Vinylmethyldiethoxysilane witht-Butyl Hypochlorite (6: 1: 1 in Presence of Catalyst To a solution of80.0 g. (0.5 mol) of vinylmethyldiethoxysilane and g. (3.0 mols) ofglacial acetic I .acid were added dropwise 54.0 g. (0.5 mol) of t-butylhypochlorite. The reaction was catalyzed by 0.5 g. of benzene-sulfonicacid. Temperature was maintained at 25to 50 by rate of addition for 2hours. The material EXAMPLE 14 Addition of Tribromophenol to an Me SiO(MeViSiO SiMe with t-BuOCl 10: l in Presence of Catalyst To a solution of99.1 g. (0.3 mol) of 2,4,6- tribromophenol and 30.7 g. (0.03 mol) ofdecavinylhexadecamethyldodecasiloxane (equilibrated) in 250 ml. ofbenzene were added 32.5 g. (0.3 mol) of t-butyl hypochlorite. Thetemperature rose 5 C. during the addition. After 5 days, the reactionwas incomplete and two drops of pyridine were added as a catalyst. Thetemperature rose 20 and within 3 hours no positive halogen was detected.After concentration, 140 g. of crude product, Me SiO(C H Br OCl-ICHClSiMeO) SiMe were isolated. (Theoretical 135 grams.)

A small amount of tribromophenol remained and was removed by triturationwith methanol. Further trituration with acetone gave a crystalline solidwhich imparted flame retardant properties to silicone rubber. A similaramount of 2,4,6-tribromophenol completely inhibited cure in the siloxanerubber.

EXAMPLE Effects of Reaction Variables on the Preparation of CF CH OCHCHClSiMe(OSiMe and CF CH OCH CHClSiEt The effects of catalysts,concentration, solvent and temperature were studied. All reactions werecarried out in washed Pyrex vessels and were protected from light. Earlyexperiments showed that soft glass was an effective catalyst for theaddition of trifluoroethanol but soft glass which had been soaked indilute hydrochloric acid and washed was not catalytic. However, Pyrexglass was not catalytic.

To a standardized solution of undecane and either 3-vinylheptamethyltrisiloxane or vinyltriethylsilane was added theappropriate quantity of trifluoroethanol. Catalyst and/or solvent, ifused, were introduced before the addition of the calculated amount oft-butyl hypochlorite. After thirty minutes the reaction mixture wasanalyzed. The findings are summarized below.

CATALYSTS For 3-vinylheptamethyltrisiloxane the following catalysts wereeffective (in decreasing order of activity, first three are nearlyequal): potassium t-butoxide, tetramethylammonium silanolate, potassiumsilanolate, pyridine, bis-triphenylphosphine platinic chloride,triphenyl phosphine, and pyridine N-oxide. Acidic materials, e.g.,benzene-sulfonic acid, trifluoroacetic acid, zinc chloride andl,3-bis(ethylene)-2,4- dichlorodichlorodiplatinum (11) causedequilibration of the siloxane and effectiveness as catalysts for theaddition could not be determined.

The addition of trifluoroethanol to vinyltriethylsilane was retarded bybenzene-sulfonic acid and cupric acetate when compared to theuncatalyzed reaction. Potassium t-butoxide was an effective catalyst.

V V CONCENTRA TIONS Time for disappearance of t-butyl hypochloriteduring the reaction of trifluoroethanol and3-vinylheptamethyltrisiloxane varied depending on the concentration oftrifluoroethanol. With a 500 percent excess, reaction time was less than30 minutes. For a percent excess, reaction time was 16 hours and for anequimolar mixture, reaction time was greater than two months.

The ratio of product to by-products showed only a slight change when theexcess of t-butyl hypochlorite was reduced from 500 percent to 0percent, i.e., it dropped from 7.0:1 to 58:1. Doubling the concentrationof the hypochlorite to the vinyl siloxane resulted in a small increasein reaction rate with a five-fold excess of trifluoroethanol but, uponstanding, acidic byproducts were detected.

The rate of reaction was not appreciably changed by increasing theconcentration of vinyl siloxane to t-butyl hypochlorite to 2:1 with a500 percent excess of trifluoroethanol over hypochlorite.

SOLVENTS Benzene, dichloromethane and nitrobenzene were found to besuitable solvents for the addition of trifluoroethanol to3-viny1heptamethyltrisiloxane. Without solvent the reactants wereinitially two phases but this did not interfere with the reaction.Acetone caused a decrease in rate of reaction.

EXAMPLE 16 Effect of Reaction Variables on the Preparation of EtOCHCHCISiMe(OSiMe and Et0CH CHC1SiEt Procedures similar to those in Example15 were used to determine the effect of variables on additions ofethanol. With 3-vinylheptamethyltrisiloxane, cupric acetate was aneffective catalyst.

Addition to vinyltriethylsilane was catalyzed by both cupric acetate andbenzene-sulfonic acid. Potassium tbutoxide catalyzed the reaction butresulted in larger amounts of by-products.

Increasing the amount of ethanol from equimolar to a five-fold excess inthe reaction with 3-vinylheptamethyltrisiloxane, resulted in an increasein rate and an increase in ratio of product to by-product from 1.6: 1 to3.2: 1. Acidic by-products, which rearrange the siloxane, result from a100 percent excess of t-butyl hypochlorite and a 500 percent excess ofethanol. Doubling the concentration of the vinyl silicon material tot-butyl hypochlorite does not appreciably affect the rate with either a100 percent or 500 percent excess of ethanol to t-butyl hypochlorite.

Both benzene and acetone were suitable solvents for the reaction ofethanol, 3-vinylheptamethyltrisiloxane and t-butyl hypochlorite.

EXAMPLE 17 Effect of Reaction Variables on the Preparation of MeOCl-l-CH,OCH CHClSiMe( OSiMe Using procedures similar to those in Example 15,the 5 effects of various conditions on the reaction of 2- methoxyethanoland 3-vinylheptamethyltrisiloxane were measured Both cupn'c acetate andcobalt (II) acetate were effective catalysts for this addition. Slightcatalytic activity was shown by both potassium t-butoxide andbenzene-sulfonic acid.

The reaction rate is increased as the concentration of the hypochloriteis increased from equimolar to a five fold excess and the ratio ofproduct to by-products increases from 1.811 to 2.5:l. With a 100 percentexcess of t-butyl hypochlorite, and a 500 percent excess of 2-methoxyethanol, acidic by-products are formed which equilibrate thesiloxane.

Reactions were carried out at 60, 0, and 78C. with little change inproduct to by-product ratio. The elevated temperature reaction showed asmall increase in reaction rate and the cooler temperature additionsexhibited a decrease in reaction rate.

EXAMPLE 18 Addition of MeOl-l, EtOH, Z-PrOH and t-BuOH to 3-Vinylheptamethyltrisiloxane A series of alcohols were added to3-vinylheptamethyltrisiloxane with t-butyl hypochlorite using theprocedures described in Example 15. Methanol was added to the siloxanein the presence of the hypochlorite to form3-[2-methoxy-1-chloroethyl1heptamethyltrisiloxane. Ethanol was added tothe siloxane in the presence of the hypochlorite to form 3[2-ethoxy-1-chloroethyllheptamethyltrisiloxane. Z-Propanol was added to thesiloxane in the presence of the hypochlorite to form3[2(2-propoxy)-lchloroethyl]heptamethyltrisiloxane. t-Butanol was addedto the siloxane in the presence of the hypochlorite to form3[2(t-butoxy)-l-chloroethyl1heptamethyltrisiloxane.

Cupric acetate was a catalyst for the reaction of 45 methanol and2-propanol. Similar rates of addition were found for methanol, ethanoland Z-propanol but for a given molar concentration of alcohol,2-propanol gave larger amounts of by-products than methanol and ethanolwhich were nearly equal. t-Butanol gave a very small amount of productand the reaction was not affected by catalysts. t-butyl hypochlorite andno added protolytic material a very small amount of QT2(tbut0xy)-l-chloroethyllheptamethyltrisiloxane is also formed.

EXAMPLE 19 Addition of Acetic Acid to Vinylsilicon Compounds Using thepreviously described procedure (Example addition of acetic acid to3-vinylheptamethyltrisiloxane with t-butyl hypochlorite to form 3[2-acetoxy-l-chloroethyl]heptamethyltrisiloxane was catalyzed by potassiumt-butoxide and was retarded by cupric acetate.

Similarly, potassium t-butoxide catalyzed the reaction of acetic acid,vir iyltriegy lsi lane and t-butyl stearamide to produce hypochlorite toform Z-acetoxy-l-chloroethyltriethylsilane with very little formation ofby-product.

EXAMPLE 20 RTV System '10 mixed with ethylene glycol and treated witht-butyl 15 trifluoroethanol to produce the respective novelorganofunctional silicon compounds listed: mnitrophenol to produce3-[2-(m-nitrophenoxy)-lchloroethyl]heptamethyltrisiloxane; 2-cyanoethylal- 20 cohol to produce 3-[2-( 2-cyanoethoxy)-l-chloroethyl]heptamethyltrisiloxane; triphenylcarbinol to produce3-[2.-(triphenylmethoxy)-l-chloroethyl1heptamethyltr isiloxane;octadecane thiol to produce3-[2-(2,2,2-octadecylthio)-l-chloroethyl]heptamethyltrisiloxane;

produce 3-[2-stearamido-l-t chloroethyl1heptamethyltrisiloxane; anilineto produce 3-[Z-anilino-l-chloroethyl]heptamethyltrisiloxane; stearicacid to produce 3-[2-stearoyl-1- chloroethyl]heptamethyltrisiloxane;benzoic acid to 3-[ Z-benzoyll -chloroethyl ]heptamethyltr isiloxane;piperidine to produce3-[2-piperidyl-lchloroethyl]heptamethyltrisiloxane; thioacetic acid toproduce 3-[2-acetylthio-l-chloroethyl]heptamethyltr isiloxane; MeO(C,HO) H to produce MeO(C,H 0)

35 CH,CHClSiMe(OSiMe p-chlorophenol to produce 3-[ 2-(p-chlorophenoxy l-chloroethyl ]heptamethyltr isiloxane; and m-nitrophenol to produce 3-[2(mnitrophenoxy)-l-chloroethyl]heptamethyl-trisiloxane.

Using the procedure of Example 9, the following protolytic compounds aresubstituted'for ethanol, using about one mol ofvinylmethyldiethoxysilane for each active hydrogen atom of theprotolytic compound, to produce the respective novel organofunctionalsilicon compounds listed: ethylene glycol to produce (EtO),MeSiCHClCI-lOCH CH,OCH=CHCl- SiMe(OEt) glycerol to produce CH CHCHJOCH,CHClSiMe(0Et) pentaerythritol to produce 50 taerythritolethyleneoxide adduct of the formula CI HZQW QMHh to ro uc I 2 2 4 H HgCHCl SiMe(OET)2]4 sorbitol to produce H20 0 OH2CHO1SiMe(0Et)2 [H OCH2CHC1SiM6(OEt)2]4 Hz 0 OHzCHClSiMMOEOz glucose to produce H20 0 CHCHClSiMe(OEt)z [H 0 CHzCHClSiMe(OEt)z]4 glycol-terminated ethyleneglycol terephthalate polyester of the formula HOCJ-IJOOCCJLCOOC, HJMeSiCHCICH OQ l9 phthalic acid to produce C H [COOCH,CHClSiMe( OEt)trimellitic acid to produce CQI'IQI COOCH CHClSiMe(OEt) acid-terminatedethylene glycol terephthalate polyester of the formula duce (EtO) MeSiCHCl CH O[OCQ H COOC H4 and siloxane polymers and copolymerscontaining the unit of the formula:

wherein a is an integer of 1 to 3; b is an integer of l to 6; c is aninteger of l to 4; d is an integer ofO to 3; the sum of c-l-d being nogreater than 4; e is an integer of l to 3; f is an integer of to 2; thesum of e-l-f being no greater than 3; R is a radical free of aliphaticunsaturation having a valence of l to 6, said valence being equal in thecase of said silanes to b times c divided by a and in the case of saidsiloxane polymers and copolymers to b times e divided by a, R beingselected from the class consisting of hydrogen, monovalent hydrocarbongroups having one to 18 carbon atoms per group, substituted monovalenthydrocarbon groups having one to 18 carbon atoms per group substitutedwith substituents from the class consisting of halogen having an atomicweight of at least 19, alkoxy, cyano, nitro and hydroxy groups;substituted monovalent hydrocarbon groups substituted with a substituenthaving the formula R O(C,,H ,,O), wherein R is a monovalent hydrocarbongroup having one to 18 carbon atoms, n is an integer of 2 to 4, and x isan integer of l to 100, and having one to 18 carbon atoms per group inaddition to those in said substituent; acyl groups having one to 18carbon atoms per group; substituted acyl groups substituted with asubstituent from the class consisting of hydroxy, alkoxy groups havingone to 18 carbon atoms per alkoxy group, and R O(C,,H ,,O) groups andhaving one to 18 carbon atoms per group in addition to those of saidsubstituent; divalent hydrocarbon groups having two to 18 carbon atoms;divalent groups of the f0rmula-(-C,.H ,,O C H divalent groups of theformula wherein R is a divalent hydrocarbon group having two to l8carbon atoms per group; divalent groups of the formula 20 RBO[CR4C orawherein R is a divalent hydrocarbon group having two to 18 carbon atomsper group; divalent groups of the formula 1 01x 0- ,l l

cn oomo divalent groups of the formula trivalent hydrocarbon groupshaving three to 18 carbon atoms per group; trivalent groups of theformula trivalent groups of the formula wherein R is a trivalenthydrocarbon group having three to 18 carbon atoms per group; tetravalenthydrocarbon groups having three to 18 carbon atoms per group;tetravalent groups of the formula hexavalent hydrocarbon groups havingfour to 18 carbon atoms per group; and hexavalent groups of the formulaormo can);-

H O C nHzn) x-" H 0 0 DH) x' H (O C nHZn) H C nHin) x Hz 0 0 DH) Y is adivalent element selected from the group consisting of O,

wherein R is selected from the group consisting of hydrogen andmonovalent hydrocarbon having one to 18 carbon atoms, and -S-; R is adivalent halogensubstituted hydrocarbon group having two to 18 carbonatoms selected from the class consisting of alkylene, cycloalkylene andalkylenearylene groups, wherein said halogen substituent has an atomicweight of at least l9 and it and said divalent element are bonded toadjacent non-aromatic carbon atoms; R" is a monovalent organic groupbonded to silicon and is selected from the class consisting ofhydrocarbon groups, alkoxy groups, aryloxy groups, substitutedhydrocarbon groups substituted with a substituent from the classconsisting of halogen having an atomic weight of at least 19, alkoxy,acyl, acyloxy, cyano, nitro and hydroxy substituents, all of said groupshaving a total of one to 18 carbon atoms per group; R (C,,H ,,O),C,,Hgroups wherein R, n and x are as defined above; and substitutedhydrocarbon groups substituted with an R O(C,,H2,.O), substituent andhaving one to 18 ca R SiR" wherein R", c and d are as defined above andR is an olefinically unsaturated monovalent group from the classconsisting of alkenyl, cycloalkenyl and alkenylaryl groups; andolefinically unsaturated siloxanes containing at least one unit of theformula:

wherein R, R", e and fare as defined above; an active hydrogen atomcontaining compound of the formula:

in the case of reaction with said olefinically unsaturated,

silane, and of the formula:

in the case of reaction with said olefinically unsaturated siloxane,wherein R, Y, a, b, c and e are as defined above; and a positive halogencompound having a posi- 4. Process as claimed in claim 1 wherein saidactive hydrogen atom containing compound is acidic and the reaction iscarried out in the presence of a basic catalyst.

5. Process as claimed in claim 1 wherein said active hydrogen atomcontaining compound is essentially neutral and the reaction is carriedout in the presence of an acidic catalyst.

6. Organofunctional silicon compounds selected from the class consistingof silanes of the formula:

wherein a is an integer of l to 3; b is an integer of l to 6;

c is an integer of l to 4; d is an integer of 0 to 3; e is an integer ofl to 3; f is an integer of 0 to 2; R is a radical free of aliphaticunsaturation having a valence of l to 6,

said valence being equal in the case of said silanes to b times cdivided by a and in the case of said siloxane polymers and copolymers tob times e dividedbya, R being selected from the class consisting of,monovalent hydrocarbon groups having one to 18 carbon atoms per group,substituted monovalent hydrocarbon groups having one to 18 carbon atomsper group substituted with substituents from the class consisting ofhalogen, alkoxy, cyano, nitro and hydroxy groups; substituted monovalenthydrocarbon groups substituted with a substituent having the formula RO(C,,H ,,O), wherein R is a monovalent hydrocarbon group having one to18 carbon atoms, n is an integer of 2 to 4, and x is an integer of 1 to100, and having one to 18 carbon atoms per group in addition to those insaid substituent; acyl groups having one to 18 carbon atoms per group;substituted acyl groups substituted with a substituent from the classconsisting of hydroxy, alkoxy groups having one to 18 carbon atoms peralkoxy group, and l R O(C,,H ,,O),- groupsand having one to 18 carbonatoms per group in addition to those of saidsubstituent; divalenthydrocarbon groups having two tg l8 carbon atoms; divalent groups of theformula A ass ..s ss ssfflafst u wherein R is a divalent hydrocarbongroups having two to 18 carbon atoms per group; divalent groups of mmwherein R is a divalent hydrocarbon having two to 18 carbon atoms pergroup; divalent groups of the formula Lil l M divalent groups of theformula trivalent hydrocarbon groups having three to 18 carbon atoms pergroup; trivalent groups of the formula trivalent groups of the formulawherein R is a trivalent hydrocarbon group having three to 18 carbonatoms per group; tetravalent hydrocarbon groups having three to 18carbon atoms per group; tetravalent groups of the formula pentavalenthydrocarbon groups having four to 18 carbon atoms per group; pentavalentgroups of the formula:

hexavalent hydrocarbon groups having four to 18 carbon atoms per group;and hexavalent groups of the formula Y is a divalent element selectedfrom the group consisting of -O,

kylene, cycloalkylene and alkylenearylene groups, wherein said halogensubstituent has an atomic weight of at least 19 and it and said divalentelement are bonded to adjacent non-aromatic carbon atoms; R" is amonovalent organic group bonded to silicon and is selected from theclass consisting of hydrocarbon groups, alkoxy groups, aryloxy groups,subsfituted hydrocarbon groups substituted with a substituent from theclass consisting of halogen having an atomic weight of at least 19,alkoxy, acyl, acyloxy, cyano, nitro and hydroxy substituents, all ofsaid groups having a total of one to 18 carbon atoms per group; R (C,.H,,O) C,,H groups wherein R, n and x are as defined above; andsubstituted hydrocarbon groups substituted with an fQiCaBaOLr ma lh v ls ns 18 c bon atoms in addition to the carbon atoms in said substituent.

7. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[2-(2,2,2- trifluoroethoxy)- lchloroethyl]heptamethyltrisiloxane.

8. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 2-(2,2,2- trifluoroethoxy)- l chloroethyltrimethylsilane.

9. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[(2,2,2trifluoroethoxy)chlorocyclohexyl]heptamethyltrisiloxane.

l0. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 2-(2,2,2- trifluoroethoxy)- l -chloroethylmethylsiloxanecyclic trimers and tetramers.

11. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[2-( lI-l,lH-perfluorooctyloxy)- l chloroethyl]heptamethyltrisiloxane.

12. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is Z-ethoxy-lchloroethylmethyldiethoxysilane.

13. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3(2-ethoxy-lchloroethyl)heptamethyltrisiloxane.

l4. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 2-ethoxy-lbromoethyltriethoxysilane.

15. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 2-(2-hydroxyethoxy)- l chloroethyltrimethylsilane.

16. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is Me SiO(C H Br OCH HClSiMeO) SiMe 17. Organofunctionalsilicon compound as claimed in claim 6 wherein said compound is2-acetoxy-lchloroethylmethyldiethoxysilane.

18. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 2-(2,2,2- trifluoroethoxy)- l chloroethyltriethylsilane.

19. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 2'ethoxy-lchloroethyltriethylsilane.

20. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[2-(methoxyethoxy l chloroethyl ]heptamethyltrisiloxane.

21. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[2-methoxy-lchloroethyl]heptamethyltrisiloxane.

22. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[2-(2-propoxy)- Y 1 -chloroethyllheptamethyltrisiloxane.

23. Organofunctional silicon compound as claimed in claim 6 wherein saidcompound is 3-[2-butoxy-lchloroethyllheptamethyltrisiloxane.

24. Organofunctional silicon compound as -[in claim 6 wherein saidcompound is 3[2-acetoxy-lchloroethyl]heptamethyltrisiloxane.

my v. CERTIFICATE OF CORRECTION p l 3,694,480 Dated Sept. 26, 1972 (3)GM. Omi etanski Inventor It is certified that error appears in theaboveident1f1ed patent and that said Letters Patent are hereby correctedas shown below:

I" v v "1 Claim 1, line 40 of column 21, that part of the formula shownas "R should read RfH o V Signed and sealed this 20th day of February1973.

(SEAL) Attest:

EDWARD NLFLETCHERJR'. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents CERTIFICATE OF CORRECTION Patent No. 3 694 Dated septa 261972 Invent -(8) I Q 1c is certified that error appears in theabove-identified patent and that said Letters Patent: are herebycorrected as shown below:

r "I Claim 1, line 40 of column 21, that part of the formula shown as "Rshould read Signed and sealed this 20th day of February 1973.

(SEAL) Attest:

EDWARD M. FLETCHER,JR O ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

2. Process as claimed in claim 1 wherein the amounts of said olefinically unsaturated silicon compound and said positive halogen compound are adequate to provide not more than about one positive halogen atom per olefinically unsaturated group of said silicon.
 3. Process as claimed in claim 1 wherein the amounts of the olefinically unsaturated silicon compound and said active hydrogen atom containing compound are adequate to provide at least one atom of active hydrogen per olefinically unsaturated group of said silicon.
 4. Process as claimed in claim 1 wherein said active hydrogen atom containing compound is acidic and the reaction is carried out in the presence of a basic catalyst.
 5. Process as claimed in claim 1 wherein said active hydrogen atom containing compound is essentially neutral and the reaction is carried out in the presence of an acidic catalyst.
 6. Organofunctional silicon compounds selected from the class consisting of silanes of the formula: Ra( (YR'')cSiR''''d) and siloxane polymers and copolymers containing the unit of the formula: wherein a is an integer of 1 to 3; b is an integer of 1 to 6; c is an integer of 1 to 4; d is an integer of 0 to 3; e is an integer of 1 to 3; f is an integer of 0 to 2; R is a radical free of aliphatic unsaturation having a valence of 1 to 6, said valence being equal in the case of said silanes to b times c divided by a and in the case of said siloxane polymers and copolymers to b times e divided by a, R being selected from the class consisting of, monovalent hydrocarbon groups having one to 18 carbon atoms per group, substituted monovalent hydrocarbon groups having one to 18 carbon atoms per group substituted with substituents from the class consisting of halogen, alkoxy, cyano, nitro and hydroxy groups; substituted monovalent hydrocarbon groups substituted with a substituent having the formula R3O(CnH2nO)x- wherein R3 is a monovalent hydrocarbon group having one to 18 carbon atoms, n is an integer of 2 to 4, and x is an integer of 1 to 100, and having one to 18 carbon atoms per group in addition to those in said substituent; acyl groups having one to 18 carbon atoms per group; substituted acyl groups substituted with a substituent from the class consisting of hydroxy, alkoxy groups having one to 18 carbon atoms per alkoxy groUp, and R3O(CnH2nO)x- groups and having one to 18 carbon atoms per group in addition to those of said substituent; divalent hydrocarbon groups having two to 18 carbon atoms; divalent groups of the formula CnH2nO)xCnH2n-; divalent groups of the formula wherein R4 is a divalent hydrocarbon groups having two to 18 carbon atoms per group; divalent groups of the formula wherein R5 is a divalent hydrocarbon having two to 18 carbon atoms per group; divalent groups of the formula divalent groups of the formula trivalent hydrocarbon groups having three to 18 carbon atoms per group; trivalent groups of the formula trivalent groups of the formula wherein R6 is a trivalent hydrocarbon group having three to 18 carbon atoms per group; tetravalent hydrocarbon groups having three to 18 carbon atoms per group; tetravalent groups of the formula pentavalent hydrocarbon groups having four to 18 carbon atoms per group; pentavalent groups of the formula:
 7. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-(2-(2,2,2-trifluoroethoxy)-1-chloroethyl)heptamethyltrisiloxane.
 8. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-(2,2,2-trifluoroethoxy)-1-chloroethyltrimethylsilane.
 9. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-((2,2,2-trifluoroethoxy)chlorocyclohexyl)heptamethyltrisiloxane.
 10. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-(2,2,2-trifluoroethoxy)-1-chloroethylmethylsiloxane cyclic trimers and tetramers.
 11. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-(2-(1H,1H-perfluorooctyloxy)-1-chloroethyl)heptamethyltrisiloxane.
 12. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-ethoxy-1-chloroethylmethyldiethoxysilane.
 13. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3(2-ethoxy-1-chloroethyl)heptamethyltrisiloxane.
 14. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-ethoxy-1-bromoethyltriethoxysilane.
 15. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-(2-hydroxyethoxy)-1-chloroethyltrimethylsilane.
 16. Organofunctional silicon compound as claimed in claim 6 wherein said compound is Me3SiO(C6H2Br3OCH2CHClSiMeO)10SiMe3.
 17. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-acetoxy-1-chloroethylmethyldiethoxysilane.
 18. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-(2,2,2-trifluoroethoxy)-1-chloroethyltriethylsilane.
 19. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-ethoxy-1-chloroethyltriethylsilane.
 20. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-(2-(methoxyethoxy)-1-chloroethyl)heptamethyltrisiloxane.
 21. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-(2-methoxy-1-chloroethyl)heptamethyltrisiloxane.
 22. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-(2-(2-propoxy)-1-chloroethyl)heptamethyltrisiloxane.
 23. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 3-(2-butoxy-1-chloroethyl)heptamethyltrisiloxane.
 24. Organofunctional silicon compound as -(in claim 6 wherein said compound is 3(2-acetoxy-1-chloroethyl)heptamethyltrisiloxane.
 25. Organofunctional silicon compound as claimed in claim 6 wherein said compound is 2-acetoxy-1-chloroethyltriethylsilane.
 26. Organofunctional silicon compound as claimed in claim 6 wherein said compound is the gelled reaction product of a siloxane fluid comprised of vinylmethyl siloxy units and dimethyl siloxy units with ethylene glycol and t-butyl hypochlorite. 